US5997625A - Coating pigment for ink-jet printing - Google Patents

Coating pigment for ink-jet printing Download PDF

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US5997625A
US5997625A US09/071,509 US7150998A US5997625A US 5997625 A US5997625 A US 5997625A US 7150998 A US7150998 A US 7150998A US 5997625 A US5997625 A US 5997625A
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composition
silica
clay
percent
calcined clay
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Michael G. Londo
Ahmad Moini
Mitchell R. Gibbs
Stephanie F. Greene
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BASF Corp
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Engelhard Corp
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Assigned to ENGELHARD CORPORATION reassignment ENGELHARD CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MOINI, AHMAD, GREENE, STEPHANIE F., LONDO, MICHAEL G.
Priority to CZ20004036A priority patent/CZ20004036A3/cs
Priority to CN99806232A priority patent/CN1127410C/zh
Priority to EP99917540A priority patent/EP1079977B1/fr
Priority to BRPI9910165-3A priority patent/BR9910165B1/pt
Priority to ES99917540T priority patent/ES2205808T3/es
Priority to DK99917540T priority patent/DK1079977T3/da
Priority to UA2000116188A priority patent/UA67771C2/uk
Priority to AT99917540T priority patent/ATE248070T1/de
Priority to PCT/US1999/008278 priority patent/WO1999056965A1/fr
Priority to DE69910767T priority patent/DE69910767T2/de
Priority to AU35635/99A priority patent/AU760107B2/en
Priority to PT99917540T priority patent/PT1079977E/pt
Priority to MYPI99001702A priority patent/MY118570A/en
Publication of US5997625A publication Critical patent/US5997625A/en
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Assigned to BASF CATALYSTS LLC reassignment BASF CATALYSTS LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ENGELHARD CORPORATION
Assigned to BASF CORPORATION reassignment BASF CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BASF CATALYSTS LLC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention is directed toward novel clay-based pigments. More particularly, the invention relates to a modified kaolin pigment useful in the coating of paper for ink-jet printing applications.
  • a further criteria is to control the contact angle of the various ink jet colors (i.e., cyan, magenta, yellow, and black) in a manner that the inks will substantially have the same contact angle when applied to the coated paper.
  • the contact angles of the various inks are substantially the same, the appearance of the ink colors are more uniform, i.e., one color does not appear more dull or more bright than another color.
  • silica is an effective paper coating constituent as a hydrophilic pigment, it is somewhat more expensive than clay-based pigments and has severe rheological limitations such as in the amount of coating solids and Brookfield viscosity.
  • U.S. Pat. No. 4,446,174 is directed to a method of ink jet recording and identifies desirable properties of substrates or coatings for satisfactory color ink jet printing.
  • This patent purports that maintaining an R f value (ratio of traveling distance of dye to that of the solvent in the aqueous ink) of less than 0.59 produces images of high quality having high ink absorption and image density.
  • the present invention relates to compositions and methods concerning clay-based pigments useful in paper coating applications, particularly in providing coatings for multicolor ink jet paper applications.
  • compositions of this invention include improved rheology and higher coating solids. This allows the high speed paper and coating machines to produce an ink-jet coated grade of paper not previously capable of being produced.
  • the material described in this invention also offers a substantial reduction in cost over the silica pigment. Yet another unexpected result is that this pigment requires less coatweight and binder than the conventional silica coatings. Also, acceptable coatings can be made without the need for dispersants.
  • FIG. 1 is a graphical illustration of this invention's advantages in terms of percent coating solids and Brookfield viscosity compared with a conventional silica pigment.
  • compositions and methods of this invention relate to novel and improved coating pigments.
  • the present invention will become more apparent from the following definitions and accompanying discussion.
  • the expression "substantially equivalent ink contact angle” is intended to define the contact angle of the various inks being within an acceptable deviation which provides the desired or acceptable print characteristics of color density and color definition. Typically, acceptable printing results are achieved when the contact angle is within ⁇ 10, more preferably ⁇ 5, most preferably ⁇ 3 degrees from the numeric average of the measured contact angles.
  • hydroxous clay is intended to describe a clay which has not been subjected to calcination, i.e., a temperature that would alter the basic crystalline structure of the clay. In the case of kaolin, subjection to temperatures under 450° C. will not alter the kaolin's crystalline structure.
  • Hydrous clays are widely known in the art and are typically produced from crude clays which have been subjected to beneficiation, as for example to, froth flotation, magnetic separation, mechanical delamination, grinding, or similar commutation.
  • Useful hydrous clays typically will have particle sizes of about greater than 80% finer than 2 micrometers.
  • Kaolinite is an aluminum hydroxide silicate having the approximate composition of Al 2 (OH) 4Si 2 O 5 .
  • a clay having the following particle size distribution characteristics has been found to provide excellent rheology: a median particle size of 0.55 micrometers and a particle size distribution such that about 88+/-2% of the particles have an equivalent spherical diameter less than about 2 micrometers and not more than about 25% by weight, preferably not more than about 20% by weight, have an equivalent spherical diameter less than 0.3 micrometers. If the quantity of ultrafine particles, i.e., particles 0.3 micrometers and finer, is too great, the rheology of the pigment may be such that it has limited, if any, use.
  • the hydrous clay In order to achieve the desired particle size distribution of the hydrous clay, it is generally necessary to perform one or more particle size separations on the crude clay.
  • processing includes degritting, followed by differential gravitational or centrifugal sedimentation to recover a size fraction of desired particle size, such as for example, a fraction that is 90% by weight finer than 2 micrometers and does not contain an excessive amount of ultrafine particles.
  • the content of ultrafines and median (weight) particle size of such fraction will vary, depending on the particle size distribution of the crude clay.
  • the clay particles are therefore treated with a deflocculant (dispersing agent) which will give all the particles a negative electric charge, and cause them to repel each other when the particles are suspended in water.
  • the clay dispersant used at this stage is generally referred to as a "primary" dispersant.
  • Dispersants used to deflocculate suspensions of previously processed clay are termed “secondary" dispersants or deflocculants.
  • Suitable dispersing agents used for primary dispersion in practice of the present invention are conventional and include water soluble salts of a condensed phosphate, such as a pyrophosphate, e.g., tetrasodium pyrophosphate, (TSPP), a water soluble salt of a polysilicic acid, for example, sodium silicate, or a water soluble organic polymeric dispersing agent, for example a polyacrylate or a polymethacrylate salt having a molecular weight in the range of about 500 to about 10,000.
  • the amount of dispersing agent used will generally be in the range of from about 0.025 to 0.2% by weight based on the weight of the dry clay.
  • particle size separations are performed using deflocculatd aqueous suspensions having a solids content of about 20-40% by weight. Other solids levels may be used to carry out such separations.
  • the median particle size of the clay particles should range from 0.4 to 0.7 micrometers, equivalent spherical diameter (e.s.d.), preferably 0.5 to 0.6 micrometers, as determined by conventional sedimentation techniques using the SEDIGRAPH® particle size analyzer, supplied by Micromeretics, Inc. From about 80% to 95% by weight of the particles should be finer than 2 micrometers, e.s.d. The content of fines below 0.3 micrometer e.s.d.
  • weight percent should be below 35 weight percent, preferably below 25 weight percent, and most preferably 20 weight percent or below. It should be understood that the measurements of the size of clay particles that are 0.3 micrometer or finer are of limited reproducibility. Thus, when a SEDIGRAPH® analyzer is employed, the value for weight percent may be +/-5% when tested by another operator or a different SEDIGRAPH® analyzer is employed. Most preferably, median particle size is 0.6+/-0.05 micrometers, e.s.d., with 85 to 90% by weight of the particles finer than 2 micrometers, e.s.d., and less than about 20% by weight or less finer than 0.30 micrometers, e.s.d. Blending of clay fractions may be advantageous or necessary with some crudes to provide a clay feed having a desirable particle size distribution.
  • a particularly preferred hydrous clay described in commonly assigned U.S. Pat. No. 5,535,890 ('890 patent), the disclosure of which is incorporated by reference.
  • Characteristic of the beneficiated hydrous clays is the ultrafine particle size distribution resulting from the described treatment of typical East Georgia crude clays.
  • the particle size typical of these crude clays varies from 80 percent (by weight) finer than 2 micrometers to in excess of 95 percent finer than 2 micrometers based on equivalent spherical diameter (e.s.d.). At least 50 percent by weight is generally finer than 0.4 micrometer.
  • these clays fall within a common definition of slimed ores, as used in froth flotation technology.
  • the beneficiated hydrous clay particularly preferred in this invention is made according to the procedure of Example 1 of the '890 patent.
  • the particle size distribution of the beneficiated clay preferably ranges from 90 percent finer than 2.0 micrometer with approximately 50-55 percent of the particles averaging 0.2 micron; more preferably 98 percent finer than 2.0 micrometer with approximately 65-70 percent of the particles averaging 0.2 micron.
  • the term "calcined” is intended to refer to heating of clay to a temperature and for a time sufficient to destroy the crystalline structure of the clay.
  • temperatures above 450° C. and for a time period which eliminates the hydroxyl groups will result in "fully calcined" product.
  • kaolinite will be fully calcined in about 1 hour. It is not desirable to heat the clay at temperatures near or above 1200° C. because severely abrasive mullite is formed which is also more difficult to leach. Also, it is difficult to leach a clay that has not been fully-calcined.
  • Ansilex® 93 pigment Characteristic of the Ansilex® 93 pigment is its higher GE brightness of 92-95 and relatively low Einlehner abrasion value of about 20 mg (i.e., low relative to other calcined kaolin clay pigments but not low compared to available non-calcined kaolin pigments).
  • Other physical characteristic of Ansilex® 93 are particle size distribution of 86 to 90 percent finer than 2.0 micrometer, median particle size of approximately 50 percent in the range of 0.6 to 0.8 micrometer.
  • the degree of leaching must not go beyond removal of more than about 40 percent by weight of the silica from the calcined clay. At silica removal amounts above 40 percent by weight, the opacity of the leached clay is adversely lowered.
  • Leaching time is dependent on several factors including:
  • the porous minerals useful in this invention are characterized in having pore sizes up to 100 Angstroms, preferably less than 40 Angstroms, most preferably less than 10 Angstroms and a BET surface area in the range of 200 to 1000 m 2 /g, preferably between 200 and 800 m 2 /g, most preferably between 400 and 800 m 2 /g. Desirably the porous minerals are uniformly porous.
  • Such minerals include zeolites, porous silica (including fumed, precipitated, aerogels, or hydrogels), alumina, calcium carbonate, montmorillonite (e.g., bentonite or hectorite), attapulgite, halloysite, vermiculite, diatomaceous earth, silicic anhydride, talc, aluminum silicate, calcium silicate magnesium silicate, barium sulfate, calcium sulfate, zinc oxide, and zirconia salt. Most preferred are zeolites.
  • Suitable natural zeolites include mordenite, clinoptilolite, ferrierite, dachiardite, chabazite, erionite, and faujasite.
  • Suitable synthetic zeolites include, but are not limited to, the synthetic faujasite crystal types, i.e. zeolites X and Y, as well as zeolites A, L, P, Beta, synthetic mordenite and ferrierite, ZSM-5, and MCM-22. Larger pore mesoporous silicates, such as MCM-41 and related phases, as well as other families of molecular sieves, such as aluminophosphates and titanosilicates, are also suitable phases.
  • a particularly preferred zeolite is any member of the faujasite family. It is to be understood that these zeolites may include demetallated zeolites which are understood to include significant pore volume in the mesoporous range, i.e. 20 to 500 Angstroms.
  • zeolites are prepared in the sodium form, that is, with a sodium cation in close proximity to each aluminum tetrahedron and balancing its charge.
  • a number of principal types of zeolites have been reported. These zeolite types vary both in their crystallographic structure as well as composition. Depending on their crystal structures, zeolites have different pore sizes. These zeolitic pores, which are present uniformly throughout the structure, should be distinguished from other non-zeolitic macropores that may be present in certain particles. Examples of approximate pore diameters include chabazite (3.8 ⁇ ), zeolite A (4.1 ⁇ ), ZSM-5 (5.1-5.6 ⁇ ), and zeolite Y (7.4 ⁇ ).
  • the composition of the zeolites may vary depending on the number of tetrahedral sites that are occupied by aluminum versus silicon. This composition is usually expressed in terms of a SiO 2 /Al 2 O 3 ratio.
  • zeolites X and Y are both synthetic analogs of the mineral faujasite, but with different composition ranges as shown below:
  • zeolites such as ZSM-5, have much higher SiO 2 /Al 2 O 3 ratios.
  • a preferred zeolite is the synthetic Y type zeolite having a faujasite structure.
  • Y type zeolite synthesized by any process can be used with no limitation.
  • Typical properties of zeolite Y used in this invention are the following:
  • substantially equivalent contact angles refer to contact angles not deviating more than ⁇ 10, preferably not more than ⁇ 5, most preferably not more than ⁇ 3 degrees from the numeric average of the contact angles measured for the multicolored inks applied to a coated paper surface containing the inventive composition of this invention. Too much deviation in contact angle will impart either loss of density or excessive bleed. Additionally, it is desirable to control the value of the contact angle between 60° and 110°, preferably between 70° and 100° most preferably between 70° and 90°. Contact angles less than 70° will tend to have poorer image density. Contact angles greater than 100° will tend to have greater bleed. The intent is to have similar contact angle responses for all the inks to achieve excellent print density and definition. If any one or combination of the four inks respond to the coating outside these ranges, the performance will be impacted. It will either tend to have bleeding of colors generated with inks that respond with greater than 100° or poorer density of colors generated with less than 70°.
  • additives may be used with the compositions of this invention to provide coating compositions.
  • additives include binders (adhesives), surfactants (dispersants), and viscosity stabilizers.
  • suitable adhesives have the ability to adsorb dyes.
  • a dye-adsorbing adhesive is a polyelectrolyte having a dissociative group capable of bonding with a dissociative group of the dyes being used.
  • the combination of a basic dye and an anionic or amphoteric polyelectrolyte, as well as the combination of a direct dye or an acid dye and a cationic or amphoteric polyelectrolyte, can be used.
  • dye-adsorbing adhesive examples include sodium polyacrylate, sodium salt of styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, polystyrene sulfonate salt, carboxymethyl cellulose, cellulose sulfate, carboxy modified polyvinyl alcohol, sodium alginate, gum arabic, emulsion of acrylic ester copolymer having an anionic dissociative group, polyvinyl benzyl trimethylammonium chloride, polydiallyl dimethylammonium chloride, polymethacryloyloxyethyl-beta-hydroxy ethyldimethylammonium chloride, hydrochloride of polydimethylaminoethyl methacrylate, polyethyleneimine, polyamide-polyamine resin, cationic starch, ethylated starch, gelatin, casein, soybean protein, acrylic acid-
  • adhesives having few or no dissociative groups may be employed.
  • starch, polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, hydroxyethylated starch, polyacrylamide, polyvinyl pyrrolidone, styrene-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, and acrylic ester copolymer emulsion may be used under such circumstances.
  • a dye-absorbing adhesive may be combined with an adhesive having no ability to adsorb dyes.
  • the binder is preferably present with the inventive composition (pigment) from about 20 to 40, more preferably from about 25 to 35 parts based on 100 parts of pigment.
  • the dye-adsorbing property of the layer of pigment can be conferred by incorporating in it a water-soluble barium salt (e.g., barium chloride), calcium salt, manganese salt or aluminum salt (e.g., aluminum chloride) which reacts with a direct dye or an acid dye in ink to form a lake, or by incorporating phosphorus tungsten molybdic acid, phosphorus tungstic acid, phosphorus molybdic acid, tannic acid, tartar emetic and aliphatic acid which reacts with a basic dye in ink to form a lake.
  • the lake formation also has the effect of providing a colored image of improved light fastness and water resistance.
  • the layer of pigment is coated from a solution which may also contain a wetting agent or surfactant such as glycerin, polyethylene glycol or pyrrolidone (rendering the pigment layer highly wettable with respect to aqueous inks), a dye or pigment (for toning such as bluing), a fluorescent dye, a UV absorber, a pigment dispersant, defoaming agent, lubricant such as calcium stearate, mildew proofing agent, and an agent for making the adhesive water-resistant such as melamine resin, urea resin, polyamide-epichlorohydrin resin, formalin, glyoxal, epoxy compound, or zirconium compound.
  • a wetting agent or surfactant such as glycerin, polyethylene glycol or pyrrolidone (rendering the pigment layer highly wettable with respect to aqueous inks), a dye or pigment (for toning such as bluing), a fluorescent dye, a UV
  • Suitable dispersants include water soluble salts of a condensed phosphate, such as a pyrophosphate, e.g., tetrasodium pyrophosphate, (TSPP), a water soluble salt of a polysilicic acid, for example, sodium silicate, or a water soluble organic polymeric dispersing agent, for example a polyacrylate or a polymethacrylate salt having a molecular weight in the range of about 500 to about 10,000.
  • a condensed phosphate such as a pyrophosphate, e.g., tetrasodium pyrophosphate, (TSPP), a water soluble salt of a polysilicic acid, for example, sodium silicate, or a water soluble organic polymeric dispersing agent, for example a polyacrylate or a polymethacrylate salt having a molecular weight in the range of about 500 to about 10,000.
  • a condensed phosphate such as a pyrophosphate,
  • the dispersant will be present in an amount of about 5 parts dispersant per 100 parts of pigment.
  • a viscosity stabilizer such as COLLOID 230 available from Rhone-Poulenc, Marietta, Ga.
  • Ammonium hydroxide such as Ammonium Hydroxide 26. Be available from any major chemical supplier
  • a (biocide) preservative such as NALCO 7649 available from Nalco Chemical, Naperville, Ill.
  • a slurry defoamer such as Dow "B” Emulsion available from Dow Corning of Midland, Mich.
  • a separate solution prepared from components other than the pigment and adhesive may be first applied to a support before it is coated with a solution containing the pigment and adhesive.
  • Suitable examples of the material that can be used as a support for the pigment coating are paper, cloth, plastic film, metal sheet, woodboard and glass sheet.
  • a transparent or translucent support enables a colored image to be observed not only by reflected light but also by transmitted light.
  • Paper used as the support in this invention is primarily made of wood pulp which may be mixed with synthetic fiber, synthetic pulp, or inorganic fiber.
  • the paper may have incorporated therein: (1) a sizing agent such as rosin, alkyl ketone dimer or alkenyl succinic acid; (2) fillers such as, silica clay, talc or calcium carbonate; (3) paper strength modifiers such as polyacrylamide or starch; (4) fixing agents such as aluminum sulfate or cationic polyelectrolyte; (5) wet strength modifiers such as melamine resin, urea resin, or polyamide-polyamine-epichlorohydrin resin; (6) dyes, including fluorescent dyes.
  • a size press may be used to apply a coating of a water-soluble adhesive such as starch, polyvinyl alcohol or gelatin.
  • the coating mixtures of the invention can be applied to the base paper sheet using coating equipment of the type generally used in the paper industry, such as a paper machine size press, or on machine and off machine coaters of various types and configurations.
  • suitable coaters include an air-knife coater, blade coater, bar coater, roll coater, gravure coater, curtain coater and metering size press.
  • the coating surface may be rendered smooth on a machine calender, supercalender or gloss calender, as in the case of general purpose pigment-coated paper. Adjustments in final solids concentration and rheological properties may be required for different coater types.
  • the coating mixture can be applied using a flexographic coater consisting of an Anilox roll and a transfer roll to apply the coating to the paper surface, which can be provided with a backing roll opposing the transfer roll.
  • the coated paper sheet can then be dried in any appropriate drying system, such as an air flotation dryer.
  • the coating weights in accordance with the invention are preferably about 4 to about 12, more preferably about 4 to about 6 g/m 2 .
  • Hydrous Clay--Commercially available hydrous clay having a particle size distribution of 90 percent less than 0.5 micrometer and a median particle size distribution of approximately 65-70 percent at 0.2 micrometer.
  • Porous Mineral---This component was a synthetic Y type zeolite having a faujasite structure (by XRD analysis) and having the following characteristics:
  • Coatings were made in a standard makedown system. That is, pigment was slurried and binder added at 40 parts per 100 parts pigment.
  • the binder used was a combination of 70 weight % polyvinyl alcohol and 30 weight % ethylated starch (Penford Gum 280 available from Penick & Ford, Cedar Rapids, Iowa).
  • Each of the coatings were applied to a base paper of 50# bond (available from Wausau/Otis) at a coating weight of between 4-5 g/m 2 .
  • the contact angles were by the method described in commonly assigned, co-pending patent application, U.S. Ser. No. 09/071,507, filed May 1, 1998 the disclosure of which is incorporated by reference and briefly described below.
  • the method involves measuring of the contact angle between each of the inks used with each coated paper.
  • a one inch by one inch sample is cut from the coated paper.
  • Each sample is then placed in a clip device to suspend the sample over the test fluid.
  • the test fluid consist of a solution of paper dyes from Clariant Corporation.
  • Brilliant Blue GNS Liquid is the cyan color
  • Red A4G New Liquid is the magenta color
  • Cartasol Yellow 3GF Liquid is the yellow color
  • Ink Black RAS liquid purified 075 is the black color. All of these colors were made into test fluids by diluting 100 microliters of the individual colors (dyes) with a sufficient amount of deionized water to achieve a total test fluid volume of 40 milliliters.
  • the resulting surface tensions of the test fluids were:
  • the clipped sample is hung in the stirrup of the Dynamic Contact Angle Analyzer instrument (Cahn DCA 315).
  • a beaker containing the test fluid is placed on the stage of the instrument directly below the test specimen.
  • the beaker is elevated manually until the test fluid is in close proximity of the test specimen.
  • the instrument program is run to raise (distance per unit time) the fluid to immerse the test specimen and subsequently remove the test specimen from the fluid.
  • the change in force is measured by the instrument.
  • the change in force over a specified distance indicates the test specimens affinity or repulsion to the particular fluid.
  • the program measures the force during the retraction of the test specimen out of the fluid. All of the measurements are then calculated by the program to give a contact angle result for each color with respect to the coated sample tested.
  • the DOS based HP Deskjet printer Dietzgen test pattern generates areas for analysis for both color density and definition.
  • Color densities are measured with a COSAR 200 densitometer with a polarized filter. Five readings are taken for each color from the approximately 1" ⁇ 1" color block generated by the printers. The readings are taken at four comers and the center of the color square, averaged and then recorded.
  • the solid color blocks are used for all the primary and combination colors. Ratings are determined by "Good”, “Slight”, and “Moderate”. The distinction for each relates to the color block edge sharpness, non-printed line sharpness (within the color blocks), in both horizontal and verticle directions. However, the test pattern has additional areas to determine black color definition. It has blocks for tone comparison. Black blocks of 1/4, 1/2, and fill tone also indicate definition. The better the tone distinction the better the definition.
  • the area of the pattern for fine definition is such that eight lines are produced, both horizontally and vertically, from a common point. They separate approximately 1 degree from each other over a distance of 1.70 inches. Therefore, the closer to the focal point each line is identifiable, the better the definition.
  • the ratings are comprised of each of these areas and given an overall definition rating.
  • a further example was completed to compare the rheological properties of the Inventive Composition with that of a conventional, silica-based, inkjet paper coating pigment (Opticil-3186 available from Huber Corporation).
  • the comparative rheological properties of the Inventive Composition and the silica in terms of the percent solids each pigment was able to be made down to and Brookfield viscosity (measured with a #2 spindle at 100 rpm and the corresponding % solids for each pigment as shown in FIG. 1) are depicted in FIG. 1.
  • the Inventive Composition (depicted as Experimental) is capable of having approximately 65% higher solids than the silica pigment (33% solids for the Experimental vs. 20% solids for the silica). Also, the Experimental composition has superior Brookfield viscosity ( ⁇ 330 cp) versus the silica ( ⁇ 450 cp) or in other words, the silica has approximately a 36% higher Brookfield viscosity than the Experimental. Clearly, the Inventive Composition characteristic of this invention has superior rheological properties compared with conventional silica pigments.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paints Or Removers (AREA)
US09/071,509 1998-05-01 1998-05-01 Coating pigment for ink-jet printing Expired - Lifetime US5997625A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US09/071,509 US5997625A (en) 1998-05-01 1998-05-01 Coating pigment for ink-jet printing
AT99917540T ATE248070T1 (de) 1998-05-01 1999-04-15 Coating-pigment für ink-jet druckverfahren
DE69910767T DE69910767T2 (de) 1998-05-01 1999-04-15 Coating-pigment für ink-jet druckverfahren
EP99917540A EP1079977B1 (fr) 1998-05-01 1999-04-15 Pigment de couche pour impression par jet d'encre
BRPI9910165-3A BR9910165B1 (pt) 1998-05-01 1999-04-15 composição de pigmento para revestimento.
ES99917540T ES2205808T3 (es) 1998-05-01 1999-04-15 Pigmento de recubrimiento para impresion por chorro de tinta.
DK99917540T DK1079977T3 (da) 1998-05-01 1999-04-15 Overtrækspigment til ink-jettrykning
UA2000116188A UA67771C2 (uk) 1998-05-01 1999-04-15 Покривний пігмент для струминного друку
CZ20004036A CZ20004036A3 (cs) 1998-05-01 1999-04-15 Nátěrový pigmentový přípravek k inkoustovému tryskovému potiskování
PCT/US1999/008278 WO1999056965A1 (fr) 1998-05-01 1999-04-15 Pigment de couche pour impression par jet d'encre
CN99806232A CN1127410C (zh) 1998-05-01 1999-04-15 用于喷墨印刷的涂层颜料
AU35635/99A AU760107B2 (en) 1998-05-01 1999-04-15 Coating pigment for ink-jet printing
PT99917540T PT1079977E (pt) 1998-05-01 1999-04-15 Pigmento de revestimento para impressao a jacto de tinta
MYPI99001702A MY118570A (en) 1998-05-01 1999-04-29 Coating pigment for ink-jet printing

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US09/071,509 US5997625A (en) 1998-05-01 1998-05-01 Coating pigment for ink-jet printing

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EP (1) EP1079977B1 (fr)
CN (1) CN1127410C (fr)
AT (1) ATE248070T1 (fr)
AU (1) AU760107B2 (fr)
BR (1) BR9910165B1 (fr)
CZ (1) CZ20004036A3 (fr)
DE (1) DE69910767T2 (fr)
DK (1) DK1079977T3 (fr)
ES (1) ES2205808T3 (fr)
MY (1) MY118570A (fr)
PT (1) PT1079977E (fr)
UA (1) UA67771C2 (fr)
WO (1) WO1999056965A1 (fr)

Cited By (25)

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EP1050413A2 (fr) * 1999-05-06 2000-11-08 Westvaco Corporation Composition de revêtement pour utilisation dans une feuille réceptrice pour l'impression par jet d'encre
US6203906B1 (en) * 1997-01-10 2001-03-20 Alcan International Limited Abrasion resistant polymer
US6378703B1 (en) 2000-11-30 2002-04-30 Engelhard Corporation Flotation method for removing colored impurities from kaolin clay
WO2002081573A1 (fr) 2001-04-03 2002-10-17 Malla Prakash B Pigments agreges a surface importante
US20030026956A1 (en) * 1999-05-21 2003-02-06 Hiroyuki Ogino Recording medium, ink jet recording method using the recording medium, and method of producing the recording medium
WO2003014039A1 (fr) * 2001-08-03 2003-02-20 Zo Resources, L.L.C. Pigment a zeolithe naturel purifie haute performance pour la fabrication et l'enduction de papier
US6585822B2 (en) * 2001-01-05 2003-07-01 Engelhard Corporation Kaolin clay glossing pigment and preparation thereof
US6610136B2 (en) 2001-04-03 2003-08-26 Thiele Kaolin Company Pigments for ink jet paper
US6641696B1 (en) 2000-07-11 2003-11-04 David A. Edgerton Method and apparatus for laminating ceramic tile
US20040255820A1 (en) * 2003-06-17 2004-12-23 J.M. Huber Corporation Pigment for use in inkjet recording medium coatings and methods
FR2856709A1 (fr) * 2003-06-26 2004-12-31 Internat Paper Sa Procede de fabrication d'un papier imprimable par jet d'encre couche directement sur une machine a papier
US20050170108A1 (en) * 1999-10-01 2005-08-04 Cabot Corporation Recording medium
US20050269050A1 (en) * 2004-05-17 2005-12-08 Klass Charles P High performance natural zeolite microparticle retention aid for papermaking
US20050282026A1 (en) * 2004-06-16 2005-12-22 Fuushern Wuu Porous coating compositions for printing applications
US20070202281A1 (en) * 2006-02-28 2007-08-30 Degussa Corporation Colored paper and substrates coated for enhanced printing performance
US20070227402A1 (en) * 2004-04-27 2007-10-04 Hui Sai H Coating-Paper Composition and Method for the Preparation Thereof
US20070237909A1 (en) * 2006-04-06 2007-10-11 Mcmanus Richard J Glossy media sheet
US20080008846A1 (en) * 2006-07-06 2008-01-10 Xiao-Qi Zhou Media sheet
US20080075869A1 (en) * 2006-09-26 2008-03-27 Degussa Corporation Multi-functional paper for enhanced printing performance
US20080187690A1 (en) * 2005-02-09 2008-08-07 Desrousseaux Stephanie V Material Intended for Forming Images by Inkjet Printing
US7544642B2 (en) 2002-12-10 2009-06-09 Halliburton Energy Services, Inc. Zeolite-containing remedial compositions
US7544640B2 (en) 2002-12-10 2009-06-09 Halliburton Energy Services, Inc. Zeolite-containing treating fluid
US20100215972A1 (en) * 2009-02-25 2010-08-26 Malla Prakash B Nano particle mineral pigment
US9944106B2 (en) 2009-04-23 2018-04-17 Hewlett-Packard Development Company, L.P Coated print media and method for making the same
WO2021071505A1 (fr) * 2019-10-11 2021-04-15 Hewlett-Packard Development Company, L.P. Composition de revêtement pour papier d'impression

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AU1006001A (en) * 2000-01-06 2001-07-12 Westvaco Corporation Glossy inkjet coated paper

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US3586523A (en) * 1968-01-15 1971-06-22 Engelhard Min & Chem Calcined kaolin clay pigment
US4446174A (en) * 1979-04-27 1984-05-01 Fuiji Photo Film Company, Ltd. Method of ink-jet recording
US4851048A (en) * 1985-07-12 1989-07-25 E.C.C. America Inc. Structured kaolin pigment and process for manufacture thereof
US4792487A (en) * 1987-03-12 1988-12-20 James River Corporation Of Virginia Ink jet recording medium comprising (a) water expansible colloidal clay (b) silica and (c) water insoluble synthetic binder
US5320897A (en) * 1992-02-18 1994-06-14 Kanzaki Paper Mfg. Co., Ltd. Ink jet recording paper and method of producing it
US5207822A (en) * 1992-04-03 1993-05-04 Ecc International Inc. Synergistic filler blends for wood-containing papers
US5535890A (en) * 1994-12-07 1996-07-16 Engelhard Corporation Method for separating mixture of finely divided minerals
US5624488A (en) * 1995-06-30 1997-04-29 Engelhard Corporation Ultrahigh brightness calcined clay pigment, manufacture & use thereof
WO1998036029A1 (fr) * 1997-02-14 1998-08-20 Ecc International Inc. Composition de revetement pour papier a impression par jet d'encre et son produit

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6203906B1 (en) * 1997-01-10 2001-03-20 Alcan International Limited Abrasion resistant polymer
EP1050413A3 (fr) * 1999-05-06 2001-09-26 Westvaco Corporation Composition de revêtement pour utilisation dans une feuille réceptrice pour l'impression par jet d'encre
EP1050413A2 (fr) * 1999-05-06 2000-11-08 Westvaco Corporation Composition de revêtement pour utilisation dans une feuille réceptrice pour l'impression par jet d'encre
US20030026956A1 (en) * 1999-05-21 2003-02-06 Hiroyuki Ogino Recording medium, ink jet recording method using the recording medium, and method of producing the recording medium
US6663922B2 (en) * 1999-05-21 2003-12-16 Canon Kabushiki Kaisha Recording medium, ink jet recording method using the recording medium, and method of producing the recording medium
US7431993B2 (en) * 1999-10-01 2008-10-07 Cabot Corporation Recording medium with glossy coating containing alumina
US20050170108A1 (en) * 1999-10-01 2005-08-04 Cabot Corporation Recording medium
US6641696B1 (en) 2000-07-11 2003-11-04 David A. Edgerton Method and apparatus for laminating ceramic tile
US6378703B1 (en) 2000-11-30 2002-04-30 Engelhard Corporation Flotation method for removing colored impurities from kaolin clay
US6585822B2 (en) * 2001-01-05 2003-07-01 Engelhard Corporation Kaolin clay glossing pigment and preparation thereof
US6610136B2 (en) 2001-04-03 2003-08-26 Thiele Kaolin Company Pigments for ink jet paper
US6478865B1 (en) 2001-04-03 2002-11-12 Thiele Kaolin Company High surface area aggregated pigments
WO2002081573A1 (fr) 2001-04-03 2002-10-17 Malla Prakash B Pigments agreges a surface importante
US6616748B2 (en) * 2001-08-03 2003-09-09 Zo Resources, Llc High performance purified natural zeolite pigment for papermaking and paper coating
WO2003014039A1 (fr) * 2001-08-03 2003-02-20 Zo Resources, L.L.C. Pigment a zeolithe naturel purifie haute performance pour la fabrication et l'enduction de papier
US6679973B2 (en) 2001-08-03 2004-01-20 Zo Resources, Llc High performance purified natural zeolite pigment for papermaking and paper coating
US7544640B2 (en) 2002-12-10 2009-06-09 Halliburton Energy Services, Inc. Zeolite-containing treating fluid
US7544642B2 (en) 2002-12-10 2009-06-09 Halliburton Energy Services, Inc. Zeolite-containing remedial compositions
US7172651B2 (en) 2003-06-17 2007-02-06 J.M. Huber Corporation Pigment for use in inkjet recording medium coatings and methods
US20040255820A1 (en) * 2003-06-17 2004-12-23 J.M. Huber Corporation Pigment for use in inkjet recording medium coatings and methods
WO2005003459A1 (fr) * 2003-06-26 2005-01-13 International Paper Sa Procede de fabrication d'un papier imprimable par jet d'encre couche directement sur une machine a papier
FR2856709A1 (fr) * 2003-06-26 2004-12-31 Internat Paper Sa Procede de fabrication d'un papier imprimable par jet d'encre couche directement sur une machine a papier
US20070227402A1 (en) * 2004-04-27 2007-10-04 Hui Sai H Coating-Paper Composition and Method for the Preparation Thereof
US20050269050A1 (en) * 2004-05-17 2005-12-08 Klass Charles P High performance natural zeolite microparticle retention aid for papermaking
US7201826B2 (en) * 2004-05-17 2007-04-10 Zo Mineral Partners Ltd. High performance natural zeolite microparticle retention aid for papermaking
US20050282026A1 (en) * 2004-06-16 2005-12-22 Fuushern Wuu Porous coating compositions for printing applications
US20080187690A1 (en) * 2005-02-09 2008-08-07 Desrousseaux Stephanie V Material Intended for Forming Images by Inkjet Printing
US20070202281A1 (en) * 2006-02-28 2007-08-30 Degussa Corporation Colored paper and substrates coated for enhanced printing performance
US8114486B2 (en) 2006-02-28 2012-02-14 Evonik Degussa Corporation Colored paper and substrates coated for enhanced printing performance
US20070237909A1 (en) * 2006-04-06 2007-10-11 Mcmanus Richard J Glossy media sheet
US10369828B2 (en) 2006-04-06 2019-08-06 Hewlett-Packard Development Company, L.P. Glossy media sheet
US20080008846A1 (en) * 2006-07-06 2008-01-10 Xiao-Qi Zhou Media sheet
US7740921B2 (en) 2006-07-06 2010-06-22 Hewlett-Packard Development Company, L.P. Media sheet
US20080075869A1 (en) * 2006-09-26 2008-03-27 Degussa Corporation Multi-functional paper for enhanced printing performance
US20100215972A1 (en) * 2009-02-25 2010-08-26 Malla Prakash B Nano particle mineral pigment
US8382016B2 (en) 2009-02-25 2013-02-26 Thiele Kaolin Company Nano particle mineral pigment
US9944106B2 (en) 2009-04-23 2018-04-17 Hewlett-Packard Development Company, L.P Coated print media and method for making the same
US10166805B2 (en) 2009-04-23 2019-01-01 Hewlett-Packard Development Company, L.P. Coated print media and method for making the same
WO2021071505A1 (fr) * 2019-10-11 2021-04-15 Hewlett-Packard Development Company, L.P. Composition de revêtement pour papier d'impression
US11718119B2 (en) 2019-10-11 2023-08-08 Hewlett-Packard Development Company, L.P. Coating composition for printing paper

Also Published As

Publication number Publication date
MY118570A (en) 2004-12-31
ES2205808T3 (es) 2004-05-01
PT1079977E (pt) 2004-01-30
EP1079977A1 (fr) 2001-03-07
ATE248070T1 (de) 2003-09-15
EP1079977B1 (fr) 2003-08-27
DK1079977T3 (da) 2003-12-01
CN1127410C (zh) 2003-11-12
WO1999056965A1 (fr) 1999-11-11
BR9910165B1 (pt) 2009-01-13
AU3563599A (en) 1999-11-23
CN1301218A (zh) 2001-06-27
AU760107B2 (en) 2003-05-08
DE69910767T2 (de) 2004-07-01
BR9910165A (pt) 2001-01-09
DE69910767D1 (de) 2003-10-02
UA67771C2 (uk) 2004-07-15
CZ20004036A3 (cs) 2002-02-13

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